D AND F BLOCK ELEMENTS

UNIT – 8
D AND f BLOCK ELEMENTS
CLASS XII

The d-block (transition metals) of the periodic table contains the

elements of the groups 3-12 in which the d orbitals are progressively
filled in each of the four long periods.
The f-block (inner transition metals) consists of elements in which 4f
and 5f orbitals are progressively filled. They are placed in a separate
panel at the bottom of the periodic table.

SERIES OF TRANSITION METALS

❖ 3d series (Sc to Zn)
❖ 4d series (Y to Cd)
❖ 5d series (La and Hf to Hg)
❖ 6d series (Ac and Rf to Cn).
SERIES OF INNER TRANSITION METALS
❖ 4f (Ce to Lu) – lanthanoids
❖ 5f (Th to Lr) - actinoids.

Transition Elements: d-Block

• The name “transition metals” was derived from the fact that their chemical
properties were transitional between those of s and p-block elements.
• According to IUPAC, transition metals are metals which have incomplete d
subshell either in neutral atom or in their ions.
• Zn, Cd, Hg of group 12 have full d10 configuration in their ground state as well
as in their common oxidation states and hence, are not regarded as transition
metals.
POSITION
The d–block occupies the large middle section of the periodic table between s– and
p– blocks. The d–orbitals of the penultimate energy level of atoms receive, i.e., 3d,
4d, 5d and 6d.
ELECTRONIC CONFIGURATION
General electronic configuration (n-1)d1–10ns1–2.
This configuration has many exceptions because of very little energy difference
between (n-1)d and ns orbitals.
D AND F BLOCK ELEMENTS

Half and completely filled sets of orbitals are more stable.

The d orbitals of the transition elements protrude to the periphery of an atom more
than the other orbitals (i.e., s and p), hence, they are more influenced by the
surroundings as well as affect the atoms or molecules surrounding them.
Ions of a given dn configuration (n = 1 – 9) have similar magnetic and electronic
properties.

3d series
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Z 21 22 23 24 25 26 27 28 29 30
4s
3d

general PROPERTIES

A. PHYSICAL PROPERTIES
• Nearly all the transition elements display metallic properties such as high
tensile strength, ductility, malleability, high thermal and electrical conductivity
and metallic lustre.
• The transition metals (except Zn, Cd and Hg) are very hard and have low
volatility.
• Except Zn, Cd, Hg and Mn, they have one or more typical metallic structures at
normal temperatures.
D AND F BLOCK ELEMENTS

MELTING AND BOILING POINTS

 High m.p and b.p.
 The high melting points of these metals are due to the
involvement of greater number of electrons from
(n-1)d along with the ns electrons in the interatomic
metallic bonding.
 In any row the melting points of these metals rise to a
maximum at d5 except for Mn and Tc and fall
regularly as the atomic number increases.

ENTHALPY OF ATOMISATION

 They have high enthalpies of atomization.

 The maxima at about the middle of each
series indicate that one unpaired electron per d
orbital is favourable for strong interatomic
interaction.
 Greater the number of valence electrons,
stronger is the resultant bonding.
 Enthalpy of atomization is an important
factor in determining the standard electrode
potential of a metal, metals with very high enthalpy of atomization are noble in
their reactions.
 The metals of the second and third series have greater enthalpies of atomization
than the corresponding elements of the first series; this accounts for the
occurrence of frequent metal – metal bonding in compounds of the heavy
transition metals.

B. ATOMIC & IONIC SIZES

• Generally, ions of the same charge in a series show decrease in radius with
increasing atomic number. Due to the new electron enters a d orbital each
time the nuclear charge increases by unity.
• The shielding effect of a d electron is not that effective, hence the net
electrostatic attraction between the nuclear charge and the outermost electron
increases and the ionic radius decreases. The variation within a series is quite
small.
D AND F BLOCK ELEMENTS

• The curves show an increase from 3d) to 4d

series but the radii of 5d series are the same
as those of the corresponding members of
the second series.
• This phenomenon is associated with the
intervention of the 4f orbitals which must be
filled before the 5d series of elements begin.
The filling of 4f before 5d orbital results in a
regular decrease in atomic radii called
Lanthanoid contraction which compensates
for the increase in atomic size with increasing atomic number.
• DENSITY:- The decrease in metallic radius with increase in atomic mass
results in a general increase in the density of elements.

C. IONISATION ENTHALPIES

First I.E1: Sc < V < Cr < Ti < Mn < Ni < Cu < Co < Fe < Zn
Second I.E2: Sc < Ti < V < Mn < Fe < Cr < Co < Zn < Ni < Cu
Third I.E3: Sc < Ti < V < Fe < Cr < Co < Mn < Ni < Cu < Zn

▪ There is slight and irregular variation in ionization energies of transition metals

due to irregular variation of atomic size.
▪ The I.E. of 5d series is higher than 3d and 4d series because of Lanthanoid
Contraction.
▪ There is an increase in I.E. along each series of the transition elements from left
to right due to an increase in nuclear charge which accompanies the filling of
the inner d orbitals.
▪ The variation in I.E. along a series of transition elements is much less in
comparison to the variation along a period of non-transition elements.
▪ The first I.E. increases, but the magnitude of the increase in the second and
third I.E. for the successive elements, is much higher along a series.
▪ A general trend of increasing values of second I.E. is expected as the effective
nuclear charge increases because one d electron does not shield another electron
from the influence of nuclear charge because d-orbitals differ in direction.
▪ However, the trend of steady increase in second and third I.E. breaks for the
formation of Mn2+ and Fe3+ respectively. In both the cases, ions have d 5
configuration.
▪ The three terms responsible for the value of I.E. are
Attraction of each electron towards nucleus
Repulsion between the electrons
D AND F BLOCK ELEMENTS

Exchange energy.
▪ Exchange energy is proportional to the total number of possible pairs of parallel
spins in the degenerate orbitals.
▪ The loss of exchange energy increases the stability. As the stability increases,
the ionisation becomes more difficult. There is no loss of exchange energy at d6
configuration.
▪ The lowest common oxidation state of these metals is +2.
▪ To form the M2+ ions from the gaseous atoms, the sum of the first and second
I.E. is required in addition to the enthalpy of atomization.
▪ The dominant term is the second I.E. which shows unusually high values for Cr
and Cu where M+ ions have the d5 and d10 configurations respectively.
▪ The value for Zn is low as the ionization causes the removal of 1s electron
which results in the formation of stable d10 configuration.
▪ In general, the third I.E. are quite high.
▪ The irregular trend in the first ionisation enthalpy of the metals of 3d series can
be accounted for by considering that the removal of one electron alters the
relative energies of 4s and 3d orbitals.
▪ Along the period in 3d series, the nuclear charge increases from scandium to
zinc but electrons are added to the orbital of inner subshell, i.e., 3d orbitals.
These 3d electrons shield the 4s electrons from the increasing nuclear charge
more effectively than the outer shell electrons can shield one another.
Therefore, the atomic radii decrease less rapidly.
▪ Thus, I.E. increase only slightly along the 3d series.
▪ Mn+ has 3d54s1 configuration and configuration of Cr+ is d5, therefore, I.E. of
Mn+ is lower than Cr+.
▪ Fe2+ has d6 configuration and Mn2+ has 3d5 configuration. Hence, I.E. of Fe2+ is
lower than the Mn2+. The third I.E. of Fe is lower than that of Mn.

D. OXIDATION STATES
 Elements with only one stable oxidation state in 3d series: Sc & Zn
 Element with max. no. of oxidation states in 3d series: Mn (+2 to +7)
 The elements which give the greatest number of O.S. occur in or near the
middle of the series.
 The lesser number of O.S. at the extreme ends is due to too few electrons to
lose or share (Sc, Ti) or too many d electrons (hence fewer orbitals available in
which to share electrons with others) for higher valence (Cu, Zn).
 Ti(IV) is more stable than Ti(III) or Ti(II).
 The maximum oxidation states of stability correspond in value to the sum of the
s and d electrons upto Mn (TiIVO2, VVO2+, CrV1O42–, MnVIIO4–) followed by a
D AND F BLOCK ELEMENTS

decrease in stability of higher oxidation states, so that the typical species to

follow are FeII,III, CoII,III, NiII, CuI,II, ZnII.
 The oxidation states in transition metals differ from each other by unity. It is
due to incomplete filling of d orbitals. e.g., VII, VIII, VIV, VV.
 However, in non-transition elements (p-block) O.S. normally differ by a unit of
two.
 In d-block (groups 4-10) higher O.S. are more preferred.
 E.g.: In group 6, Mo(VI) and W(VI) are found to be more stable than Cr(VI). Thus
Cr(VI) in the form of dichromate in acidic medium is a strong oxidizing agent,
whereas MoO3 and WO3 are not.
 Low O.S. are found when a complex compound has ligands capable of π-
acceptor character in addition to the σ-bonding.
 e.g: Ni(CO)4 – O.S. of Ni = 0
Fe(CO)5 - O.S. of Fe = 0.

E. TRENDS IN THE M2+/M STANDARD ELECTRODE

POTENTIALS
▪ Cu having a positive E0, accounts for its
inability to liberate H2 from acids.
▪ Only oxidizing acids (HNO3 and hot conc.
H2SO4) react with Cu, the acids being reduced.
▪ The high energy to transform Cu(s) to Cu2+(aq)
is not balanced by its hydration enthalpy.
▪ The general trend towards less negative E0 values
across the series is related to the general increase
in the sum of the first and second I.E.
▪ The value of E0 V for Mn, Ni and Zn are more negative than expected from the
trend.
▪ The stability of the half-filled d sub-shell in Mn2+ and the completely filled d10
configuration in Zn2+ are related to their E0 values, whereas E0 for Ni is related
to the highest negative ∆hydH.
D AND F BLOCK ELEMENTS

F. TRENDS IN THE M3+/M2+ STANDARD ELECTRODE

POTENTIALS
❖ The low value for Sc is due to the stability of Sc3+ which has a noble gas
configuration.
❖ The highest value for Zn is due to the removal of an electron from the stable d10
configuration of Zn2+.
❖ The comparatively high value for Mn shows that Mn2+(d5) is stable, whereas
comparatively low value for Fe shows the extra stability of Fe3+ (d5).
❖ The low value for V is related to the stability of V2+ (half-filled t2g level).
G. Chemical Reactivity and E0Values
 The metals of the first series except for copper are relatively more reactive and
are oxidised by 1M H+, though the actual rate at which these metals react with
oxidising agents like hydrogen ion (H+) is sometimes slow.
 For example, titanium and vanadium are passive to dilute non oxidising acids at
room temperature.
 The E0 V values for Mn, Ni and Zn are more negative from the general
trend.
 Whereas the stabilities of half-filled d subshell (d5) in Mn2+ and completely
filled d subshell (d10) in zinc are related to their E e values; for nickel, E value
is related to the highest negative enthalpy of hydration.
 Mn3+ and Co3+ ions are the strongest oxidising agents in aqueous solutions.
 The ions Ti2+, V2+ and Cr2+ are strong reducing agents and will liberate
hydrogen from a dilute acid,
e.g., 2 Cr 2+(aq) + 2 H+(aq) → 2 Cr 3+(aq) + H2(g)

H. TRENDS IN STABILITY OF HIGHER OXIDATION STATES

HALIDES
➢ The highest oxidation numbers are in TiX4 (tetrahalides), VF5 and CrF6.
➢ Mn does not have a +7 state in simple halides.But MnO3F is known.
➢ Beyond Mn no metal has a trihalide except FeX3 and CoF3.
➢ The ability of fluorine to stabilize the highest O.S. is due to higher lattice
energy (CoF3) or higher bond enthalpy terms for the higher covalent
compounds, e.g., VF5 and CrF6.
➢ Although V+5 is represented only by VF5, the other halides undergo hydrolysis
to give oxohalides, VOX3.
➢ Another feature of fluorides is their instability in the low oxidation states e.g.,
VX2 (X = CI, Br or I) and the same applies to CuX.
➢ All CuII halides are known except the iodide.
2Cu2+ + 4I- → Cu2I2 (s) + I2
D AND F BLOCK ELEMENTS

➢ Many copper (I) compounds are unstable in aqueous solution and undergo
disproportionation.
2Cu+ → Cu2+ + Cu
➢ The stability of Cu2+ (aq) than Cu+(aq) is due to the more negative ∆hydH of
Cu2+ (aq) than Cu+, which compensates the second I.E of Cu.

OXIDES

➢ The highest oxidation number in the oxides coincides with the group
number and is attained in Sc2O3 to Mn2O7.

➢ Beyond Group 7, no higher oxides of Fe above Fe2O3, are known, although

ferrates (VI)(FeO4)2–, are formed in alkaline media but they readily decompose
to Fe2O3 and O2.
➢ Oxocations stabilise Vv as VO2+, VIV as VO2+ and TiIV as TiO2+
➢ The ability of oxygen to stabilize these high oxidation states exceeds that of
fluorine.
➢ Thus the highest Mn fluoride is MnF4 whereas the highest oxide is Mn2O7.
➢ In the covalent oxide Mn2O7, each Mn is tetrahedrally surrounded by O’s
including a Mn–O–Mn bridge.
➢ The tetrahedral [MO4] ions are known for VV, CrVl, MnV, MnVl and MnVII.

I. MAGNETIC PROPERTIES
➢ When a magnetic field is applied to substances, two types of magnetic
behaviour are observed: diamagnetism and paramagnetism.
D AND F BLOCK ELEMENTS

➢ Diamagnetic substances are repelled by the applied field.

➢ Paramagnetic substances are attracted.
➢ Substances which are attracted very strongly are ferromagnetic.
➢ Ferromagnetism is an extreme form of paramagnetism.
➢ The magnetic moment increases with the increasing number of unpaired e-.
➢ Paramagnetism arises from the presence of unpaired electrons.
➢ Magnetic moment is die to orbital and spin angular momentum, In 3d series,
only spin momentum is significant.
μ = √𝒏 (𝒏 + 2) (n – no. of unpaired electrons)
Unit is BM (Bohr Magneton)
n μ (BM)
0 0
1 1.73
2 2.84
3 3.87
4 4.90
5 5.92

J. FORMATION OF COLOURED IONS

➢ Transition metals exhibit coloured ions due to presence of unpaired d-
electrons.
➢ When an electron from a lower energy d -orbital is excited to a higher energy
d-orbital (d-d transition) the energy of excitation corresponds to the
frequency of light absorbed. This frequency generally lies in the visible region.
➢ The colour observed corresponds to the complementary colour of the light
absorbed.
➢ The frequency of the light absorbed is determined by the nature of the ligand.

➢ For example, hydrated cupric ion absorb red light and the transmitted light is
greenish blue light. Hence the compound of Cu+2 ions show greenish-blue
colour.
D AND F BLOCK ELEMENTS

➢ Titanium in [Ti(H2O)6]3+ has one electron in its d- orbital (3d1)which can

absorb energy corresponding to yellow wavelength and the solution will
appear purple colour.

K. FORMATION OF COMPLEX COMPOUNDS

▪ Complex compounds are those in which the metal ions bind several anions or
neutral molecules giving complex species with characteristic properties.
▪ E.g.: [Fe(CN)6]3–, [Fe(CN)6]4–, [Cu(NH3)4]2+ and [PtCl4]2–
▪ The transition metals form many complex compounds. This is due to the
smaller sizes of the metal ions, their high ionic charges and the availability of d
orbitals for bond formation.

L. CATALYTIC PROPERTIES
• Transition metals have catalytic properties because of their ability to adopt
multiple oxidation states, large surface area and form complexes.
• E.g.: V2O5 (Contact Process), finely divided Fe (Haber’s Process), Ni (in
Catalytic Hydrogenation).
• Catalysts at a solid surface involve the formation of bonds between reactant
molecules and atoms of the surface of the catalyst.
• This increases the concentration of the reactants at the catalyst surface and
weakens the bonds in the reacting molecules (lowering of activation energy).
• For example, Fe (III) catalyzes the reaction between iodide and persulphate
ions.
D AND F BLOCK ELEMENTS

M. FORMATION OF INTERSTITIAL COMPOUNDS

• Interstitial compounds are formed when small atoms like H, C or N are trapped
inside the crystal lattices of metals.
• They are usually non-stoichiometric and are neither ionic nor covalent.
• E.g: TiC, Mn4N, Fe3H, VH0.56 and TiH1.7, etc.

Physical & Chemical Characteristics

 Higher m.p than pure metals.
 Very hard, some borides approach diamond in hardness.
 Retain metallic conductivity.
 Chemically inert.

N. ALLOY FORMATION
• An alloy is a homogeneous solid solution in which the atoms of one metal are
distributed randomly among the atoms of the other.
• Transition metals form alloys because of similar radii and physical properties
of transition metals.
• The alloys are hard and have high melting points.
• E.g: ferrous alloys: Cr, V, W, Mo, Mn are used to produce steels and stainless
steel, brass (Cu-Zn) and bronze (Cu-Sn).

Inner Transition Elements: f block

Lanthanoids
At.
Element Symbol
Electronic configuration Unpaired electrons
no.
57 Lanthanum La [Xe]4f05d16s2
58 Cerium Ce [Xe]4f15d16s2
59 Praseodymium Pr [Xe]4f05d16s2
60 Neodymium Nd [Xe]4f05d16s2
61 Promethium Pm [Xe]4f05d16s2
62 Samarium Sm [Xe]4f05d16s2
63 Europium Eu [Xe]4f05d16s2
64 Gadolinium Gd [Xe]4f05d16s2
65 Terbium Tb [Xe]4f05d16s2
66 Dysprosium Dy [Xe]4f05d16s2
67 Holmium Ho [Xe]4f05d16s2
68 Erbium Er [Xe]4f05d16s2
69 Thulium Tm [Xe]4f05d16s2
D AND F BLOCK ELEMENTS

70 Ytterbium Yb [Xe]4f05d16s2
71 Lutetium Lu [Xe]4f05d16s2

Electronic Configuration
General electronic configuration: (n-2)f1-14(n-1)d1-2ns1-2
Atoms of these elements have electronic configuration with 6s2 common but with
variable occupancy of 4f level.
The electronic configurations of tripositive ions (the most stable O.S of
lanthanoids) are of the form 4f n (n = 1 to 14).

Atomic and Ionic Sizes

➢ Lanthanoid contraction: The overall decrease in atomic and ionic radii from
La to Lu due to poor shielding effect of 4f electrons, which decrease the
attraction between nucleus and outermost electrons.
➢ Consequence: The almost identical radii of Zr (160 pm) and Hf (159 pm).
➢ The decrease in atomic radii is not quite regular as it is regular in M3+ ions.
➢ This contraction is similar to that observed in an ordinary transition series and is
attributed to the same cause, the imperfect shielding of one electron by another
in the same sub-shell.
➢ The shielding of one 4 f electron by another is less than one d electron by
another with the increase in nuclear charge along the series.
➢ There is fairly regular decrease in the sizes with increasing atomic number.
➢ The cumulative effect of the contraction of the lanthanoid series, known as
lanthanoid contraction, causes the radii of the members of the third transition
series to be very similar to those of the corresponding members of the second
series.
Oxidation State
• La(II) and Ln(III) compounds are predominant species.
• Occasionally +2 and +4 ions in solution or in solid compounds are also
obtained. This irregularity arises due to extra stability of empty, half-filled or
filled f subshell.
• The formation of Ce(IV) is favoured by its noble gas configuration, but it is a
strong oxidant reverting to the common +3 state.
• The E o value for Ce4+/ Ce3+ is + 1.74 V {=>it can oxidize water}. However,
the reaction rate is very slow and hence Ce(IV) is a good analytical reagent.
• Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides, MO2.
• Eu2+ is formed by losing the two s electrons and its f 7 configuration accounts
for the formation of this ion. Eu2+ is a strong reducing agent changing to the
common +3 state.
D AND F BLOCK ELEMENTS

• Yb2+ which has f14 configuration is a reductant.

• Tb(IV) has half-filled f-orbitals and is an oxidant.
• Sm and Eu exhibit both +2 and +3 oxidation states.

General Characteristics
❖ PHYSICAL NATURE: All the lanthanoids are silvery white soft metals and
tarnish rapidly in air.
❖ HARDNESS: The hardness increases with increasing atomic number, Sm is
steel hard.
❖ m.p: Their m.p range between 1000 - 1200 K but Sm melts at 1623 K.
❖ CONDUCTORS: They have typical metallic structure and are good conductors
of heat and electricity.
❖ DENSITY: change smoothly except for Eu and Yb and occasionally for Sm and
Tm.
COLOUR: Many Ln+3 ions are coloured both in the solid state and in aqueous
solutions. Colour of these ions may be attributed to the presence of f electrons.
Absorption bands are narrow because of the excitation within f level.
Exception: La3+ and Lu3+ ions do not show any colour.
❖ MAGNETISM: The lanthanoid ions other than the f0 type (La3+ and Ce4+)
and the f14 type (Yb2+ and Lu3+) are all paramagnetic.
❖ E0 Values
For E0 V for the half-reaction:
Ln3+(aq) + 3e– → Ln(s) are in the range of –2.2 to –2.4 V except for Eu for
which the value is – 2.0 V.

USES:
• Production of alloy steels for plates and pipes.
• A well-known alloy is mischmetall which consists of a lanthanoid metal (~
95%) and iron (~ 5%) and traces of S, C, Ca and Al.
• Mischmetall is used in Mg-based alloy to produce bullets, shell and lighter flint.
• Mixed oxides of lanthanoids are employed as catalysts in petroleum cracking.
• Some individual Ln oxides are used as phosphors in television screens and
similar fluorescing surfaces.

Applications of d and f block elements

➢ Iron and steels are the most important construction materials. Their production
is based on the reduction of iron oxides, the removal of impurities and the
addition of carbon and alloying metals such as Cr, Mn and Ni.
➢ TiO is manufactured for the pigment industry
D AND F BLOCK ELEMENTS

➢ MnO2 is manufactured for use in dry battery cells. The battery industry also
requires Zn and Ni/Cd.
➢ Coinage metals (Group 11 elements): Ag and Au are restricted to collection
items and the contemporary UK ‘copper’ coins are copper-coated steel. The
‘silver’ UK coins are a Cu/Ni alloy.
➢ Catalysts:
 V2O5 catalyzes the oxidation of SO2 in the manufacture of sulphuric acid.
 TiCl4 with A1(CH3)3 - Ziegler catalysts used to manufacture polyethylene
(polythene).
 Fe catalysts are used in Haber process.
 Ni catalysts enable the hydrogenation of fats to proceed.
 PdCl2 is a catalyst in Wacker process (oxidation of ethyne to ethanal).
 Nickel complexes are useful in the polymerization of alkynes and benzene.
➢ The photographic industry relies on the special light-sensitive properties of
AgBr.